Azo compounds and process for coloring therewith



- ing coloration.

Patented June 18, 1940 UNITED STATES PATENT OFFICE AZO COMPOUNDS ANDPROCESS FOR COLORING THEREWI'I H James G. McNally and Joseph B. Dickey,Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey No Drawing. Application November 12, 1938,

Serial No. 240,115

7 Claims.

Organic derivatives of cellulose are character ized by an indifierentaffinity for the usual cot-,

ton and "wool dyes especially the ordinary water soluble dyes. Becauseof this, it has been necessary to develop new dye compounds suitable forthe dyeing or coloration of materials, such as textile materials, madeof or containing an organic derivative of cellulose. It is, accordingly,i an object of our invention to provide a new class of aromatic azo dyessuitable for the dyeing or coloration of organic derivatives ofcellulose. Another object is to provide a process for the coloration oforganic derivatives of cellulose in which the dye or dyes are applieddirectly from an aqueous suspension to the material undergo- A furtherobject is to produce dyeings on organic derivatives of cellulose whichare of good fastness to light and washing. Other unhydrolyzed mixedorganic acid estersof cellulose such as cellulose acetate-propionate,cellulose acetate-butyrate, and the cellulose others such as methylcellulose, ethyl cellulose, or benzyl cellulose. While our inventionwillbe illustrated more particularly inlconnection with the colorationof cellulose acetate, a material to which the invention is especiallyadapted, itwill j be understood that it applies to the coloration ofother organic derivatives of cellulose such as those just mentioned. I

The azo dye compounds of our invention have the general formula:

O-Ra

wherein, R represents the residue of an aromaticnucleus, R1 andRz eachrepresents a member selected from the group consisting of hydrogen,

an alkyl group, an allyl group, a cycloalkyl group, an aryl group and aheterocyclic group, R3 repre sents the residue of a benzene nucleuswhich" may be substituted and A meansthe benzene nucleus so designatedmay be substituted. The benzene nucleus designated A, however, shouldnot contain a nuclear sulfonic acid group.

It will be understood that alkyl, as used herein, unless otherwisestated, includes not only runsubstituted alkylgroups, such as a methylgroup, an ethyl group or a propyl group but also substituted alkylgroups such a s-hydroxyethyl, li -hydroxypropyl, {3-methoxyethy1 or,B-ethoxyethyl, for example. Illustrative of cycloalkyl may be mentionedcyclohexyl.

The azo dye compounds of our invention can be prepared by diazotizing asuitable primary aromatic amine and coupling the diazonium compoundobtained with a coupling compound having the general formula:

wherein A, R1, R2 and R3 have the meaning pre viously assigned to them.I

'.-As previously indicated, the nuclear non-sulfonated aromatic azo dyecompounds of our invention constitute valuable dyes for the colorationof organic derivatives of cellulose such as those hereinbeforementioned, yielding various shades thereon of good fastness to light andwashing. These nuclear non-sulfonated dye compounds likewise possessapplication for the dyeing of wool and silk and yield generally similarshades on these materials as on organic derivatives of cellulose.Compounds in which the aromatic nucleus designated R contains a nuclearsulfonic acid group can likewise be prepared in known fashion. Thesecompounds possess little or no utility for the coloration of organicderivatives of cellulose but can be employed to color textile materialssuch as wool and silk, yielding various shades thereon.

lulose acetate silk, nuclear non-sulfonated' compounds wherein R is aphenyl residue are generally advantageous. Said phenyl residue may besubstituted as clearly shown herein.

The following examples illustrate the prepara tion of the azo dyecompounds of our invention.

Example 1 13.8 grams of p-nitroaniline are diazotized in the usualmanner and the diazonium compound obtained is added slowly to a coldhydrochloric acidsolution of 18.5 grams of m-amino-diphenyl ether.Coupling is completed by adding sodium For the dyeing of organicderivatives of cellulose such as celacetate. The dye is filtered, washedand dried.

The dye compound obtained colors cellulose acetate silk a red shade.

Example 2 The diazo solution of Example 1 is coupled with one equivalentof m-fi-hydrooryethylamino diphenylether as in Example 1. The dyecompound obtained colors cellulose acetate silk a red shade:

Example 3 One gram mole of p-nitro-o-chloroahiline is diazotized and thediazonium compound obtained is coupled with one gram mole ofm-di-o-hydroxyethylamino diphenylether'as in Example 1. The dye compoundobtained colors'cellulose acetate silk a rubine shade.

Example 4 One gram mole of p-nitro-o-bromoaniline is diazotized and thediazonium compound obtained is coupled with one gram mole of in a colddilute sodium carbonate solution. The dye is salted out, filtered,Washed and dried. It colors cellulose acetate silk a rubine shade.

Example 5 One gram mole of o-chloroaniline is diazotized in the usualmanner and the diazonium compound obtained is coupled with one gram moleof The dye compound obtained colors cellulose acetate sill: a yellowshade.

Eatample 6 diazotized and the diazo'nium compound obtained is coupledwith one gram mole of as in Example 1. The dye compound obtained colorscellulose acetate silk an orange shade.

Example 7 One gram mole of 2,4-dinitroaniline is diazotized and thediazonium compound obtained is coupled with one gram mole ofm-di-fi-hydroxyethylaminodiphenyl ether as in Example 1. The dyecompound obtained colors cellulose acetate silk 2. wine shade.

Example 8 One gram mole of 2,4-dinitro-G-chloroaniline is diazotized andthe diazonium compound obtained is coupled with one gram mole of actionsmay, for example, be carried out following the general proceduredescribed 7 in Examples 1 to 8, inclusive.

. Color on Amine Coupling component cellulose acetate silk o-(Ol, Br,l)-aniline 1. m-amino diphenyl ether Yellow. Do 2. m-fi-hydroxyethylamino diphenyl ether Do. 3. m-glyceryl amino diphenyl ether Do.

. m-B sulfo ethyl amino diphenyl ether Do. m-cetyl amino dipheny etherDo. m-di-fl-hydroxyethyl amino diphenyl ether Do. m-di-glyceryl aminodiphenyl ether Do. mdi-'y-chloro-fl-hydroxypropyl amino diphenyl etherDo.

. m-B-hydroxyethyl glyceryl amino diphenyl ethen Do.

0. m-fl-hydroxyethyl ethyl amino diphenyl etherx-.. Do.

. m-glyceryl ethyl amino diphenyl et er Do.

. m-fi-cetyl sulioethyl amino diphenyl other- Do.

. m-benzyl sulfatoethyl amino diphenyl ether D0,

O OH

CH: cyolohexyl 0 I ONa p-Nitroaniline 1-14 above Red. p-Nitro-o-(F, Cl,Br, I) aniline" do Rubine. 2,4-dinitroaniline .rlo Wine.2,4-dinitro-6-bromo (chloro) aniline -d Violet. 2,4,6-trinitroaniline doRed-blue. p-Aminoazobenzene.. J Orange-red. p-Aminoacetophenon d0Orange.

It will be understood that the foregoing exam ples and tabulationshowing the preparation of various azodye compounds "included within thescopeof our invention are intended to be illustrative and not limitativeof the invention. To illustrate, the benzene nucleus which has beendesignated A may contain substitutentsinaddition to those shown in thecompounds of the examples and tabulation. This benzene nucleus may alsobe substituted, for example, with an alkyl groupsuch as ethyl orprop'yl, an alk'oxygroup such as methoxy or ethoxy, a nitro group and ahalogen atom such as chlorine and bromine.

In order that the preparation of the azo dye compounds of our inventionmay be clearly un-, derstood, the preparation of various couplingcomponents which may be employed in their manufactureis describedhereinafter. The coupling components of the present invention can beprepared with comparative ease from chemicals which can be prepared at alow cost by either one of the following reactions. In the first methodof preparation, a nitro-benzene nucleus containing a halogen atom in them-position to the nitro group is reacted with an alkali metal phenolateand the compound prepared by this re action is then reduced by standardreduction methods to convert the nitro group to an amino group. .{Ihecompound resulting from this reduction may then be treated in knownfashion to introduce the substituent groups, other than hydrogen,represented by R1 and R2. The main reactions in connection with thisfirst method may be indicated as follows:

I. QNOz+O-alkali metal halogen The second method of preparing thecoupling s reduce 1 1 1 N02 components employed in the preparation ofthe azo dye compounds of our invention is to react m-halogenaniline withan alkali metal phenolate as indicated hereinafter: a

11.. ONHz+C -O-a1kalimetal halogen The compound thus obtained may betreated in known fashion to introduce the substituents reprequire theuse of a dispersing or solubilizing agent but may be applied to silk,wool and (depending upon the nature and position of thewater-solubilizing group) organic derivatives of cellulose textilematerials from an aqueous solution of the dye which may contain salt.For a more complete description as to how the azo dye com:

pounds of our invention maybe employed in dye ing or coloringoperations, reference may be had to our U. S. Letters Patent No.2,115,030, issued April 26, 1938. For a more detailed description as tohow the water soluble azo dyes of our invention may be employed for thecoloration of textile materials made of or containing organicderivatives of cellulose, silk and Wool or mixtures of these, referencemay be had to our U. S. Letters Patent No. 2,107,898, issued February 8,1938.

We claim:

1. The azo dye compounds having the general formula:

O R3 wherein R. represents the residue of an aryl nucleus of the benzeneseries, B representsthe residue of an aryl nucleus of the benzeneseriescontaining but one benzene ring, R1 and R2 each represents a memberselected from the group consisting of hydrogen, an alkyl group, an allylgroup, a cycloalkyl group, an aryl group and a heterocyclic group, Rarepresents the residue of an aryl nucleus of the benzene seriescontaining but one benzene ring and wherein the .wherein It representsthe residue of an aryl nucleus of the benzene series, B represents theresidue of an aryl nucleus of the benzene series containing but onebenzene ring, R3 represents the residue of an aryl nucleus of thebenzene series containing but one benzene ring, wherein the and the O-Rsgroupings are attached to the benzene nucleus B in para and orthoposition,

respectively, to the azo bond and wherein each of the hydrogen atomsattached to the nitrogen atom of the group may be'repla-ced with analkyl group.

3. 'The'azo dye compounds having the general formula:'

O R wherein R represents the residue of an aryl nucleus of the benzeneseries containing but one benzene ring, R1 and Rzleach represents amember selected from the group consisting of hydrogen, an alkyl group,an allyl group, a cycloalkyl group, an aryl group and a heterocyclicgroup and R3 represents the residue of an aryl nucleus.

of the benzene series containing but one benzene ring.

4. The azo dye compounds having the general formula:

wherein R and Breach represents the residue of an aryl nucleus of thebenzene series containing but one benzene ring and wherein each of thehydrogen atoms attached to the nitrogen atom may be replaced by an alkylgroup. 5. Material made of or containing an organic derivative ofcellulose colored with a nuclear non-sulfonated azo dye compound havingthe general formula:

and the O--Rs groupings are attached to the benzene nucleus B in paraand ortho position, respectively, to the azo bond.

' 6. A cellulose acetate colored with a nuclear nonsulfonated azo dyecompound having the general formula:

wherein R represents the residue of an aryl nucleus of the benzeneseries, B represents the residue of an aryl nucleus of the benzeneseries containing but one benzene ring, R1 and R2 each represents amember selected from the group consisting of hydrogen, an alkyl group,an allyl group, a cycloalkyl group, an aryl group and a heterocyclicgroup, R3 represents the residue of an aryl nucleus of the benzeneseries containing but one benzene ring and wherein the and the OR3groupings are attached to th benzene nucleus B in para and orthoposition, respectively, to the azo bond.

7. A cellulose acetate colored with a nuclear nonsulfonated azo dyecompound having the general formula:

v OR3 wherein R represents the residue of an aryl nucleus of the benzeneseries, B represents the residue of an aryl. nucleus of the benzeneseries containing but one benzene ring, R3 represents the residue of anaryl nucleus of the benzene series containing but one benzene ring,wherein the and the --OR3 groupings are attached to the benzene nucleusB in para and ortho position, respectively, to the azo'bond and whereineach of the hydrogen atoms attached to the nitrogen atom of the 2 groupmayfbe replaced with an alkyl group.

JALIES G. MCNALLY. JOSEPH B. DICKEY.

